JP2012517517A - Polymer composition containing nanoparticulate IR absorber - Google Patents

Abstract

  The present invention relates to a method for producing a polymer composition with a nanoparticulate IR absorber preparation, as well as to a polymer composition produced by this method. The use of this polymer composition for example in thermal management or agriculture is likewise an object of the present invention. A further subject of the present invention is a molded part, in particular a sheet containing said polymer composition.

Description

  The present invention relates to a method for producing a polymer composition using a nanoparticulate IR absorber preparation, as well as to the polymer composition thus produced. The use of such polymer compositions, for example in heat management or in agriculture, in particular as greenhouse sheets, is likewise an object of the present invention. A further subject of the present invention is a shaped body, in particular a sheet, containing such a polymer composition.

  Furthermore, embodiments of the invention can be ascertained from the claims, the description and the examples. The above-mentioned features of the subject matter according to the invention, as well as the features that are still to be explained below, can be used in each case specifically described in the combination, and other combinations without departing from the scope of the invention. Can also be used. Preferred or highly preferred are embodiments of the invention in which all features are preferred or have a highly preferred meaning.

  EP 1 554 924 A1 describes thermal radiation shielding materials in the field of agriculture or landscaping. Such a material has a layer composed of a resin base material and a fine particle filler dispersed in the resin. The fine particles are, for example, lanthanum hexaboride or antimony-doped tin oxide.

  EP 1 865 027 A1 describes a polycarbonate composition containing metal boride fine particles. Molded bodies composed of such polycarbonate compositions described in EP 1 865 027 A1 can be used as materials for windows and roofs or as sheets in agriculture.

  GB 2 014 513 A describes a transparent thermoplastic laminate that can be used as a greenhouse material. The laminate has at least two layers, where the bottom layer is highly UV resistant and the other layers are impermeable to IR radiation.

  Allingham in US 4,895,904 describes polymer plates or foils and their use in greenhouses. Such plates or sheets contain fine particle components that are absorptive or reflective in the NIR region. These plates or sheets are transparent to at least 75% of the light rays involved in photosynthesis. As the fine particle component, an oxide or a metal is used. Furthermore, a UV stabilizer is contained in the plate or sheet.

  When excessively exposed to heat, particularly sunlight, for example, through the surface of a building, car, warehouse, or greenhouse, the internal temperature often increases significantly, especially in areas where the amount of solar radiation is high. This increase in thermal action negatively affects the harvest of plants protected in the greenhouse.

  However, it is often desirable that other regions of the solar spectrum are not attenuated as well due to the blockage of heat radiation. In particular, when blocking heat irradiation by a greenhouse sheet, in addition to effective blocking of heat irradiation, high transparency in the visible spectrum range is required, especially in the visible spectrum range, this is the process of plant photosynthesis. Is important to. Thus, in this very application, very little turbidity of the material due to thermal protection is tolerated. This is because even a slight increase in transparency usually leads to a clear increase in yield.

  The object of the present invention is therefore to provide a shield against thermal irradiation, particularly against solar radiation, for example on the surface of a greenhouse, in the action of light, and also with high transparency to visible light and at the same time effective thermal irradiation shielding. Is to guarantee.

These and other issues will be described in the following method steps a. Producing a polymer melt,
b. Producing a preparation comprising a liquid carrier medium and a nanoparticulate IR absorber dispersed therein;
c. Mixing the polymer melt (a) with the preparation (b);
d. Processing the mixture (c);
It is solved by a method for producing a polymer composition having

  In the sense of the present application, nanoparticulate IR absorbers are particles having a mass average particle diameter of generally at most 200 nm, preferably at most 100 nm. A preferred particle size range is 4 to 100 nm, especially 5 to 90 nm. Such particles are usually characterized by having a high uniformity with respect to their size, size distribution, and morphology. Here, the particle size can be measured, for example, by UPA (Ultrafine Particle Analyzer), for example, by laser scattering (laserlight back scattering).

  In the IR range (about 700-12000 nm), preferably in the NIR range of 700-1500 nm, particularly preferably in the range of 900-1200 nm, nanoparticulate IR absorbers have a significant absorption. In the visible spectral range of about 400 nm to 760 nm, nanoparticulate IR absorbers have only a slight absorption.

  In general, if something behind the material is relatively clearly visible, the material is transparent (eg, glazing). In the scope of the present invention, transparency means optical transparency in which almost no light is scattered through a transparent material in the visible spectral range.

  For the measurement of turbidity (Haze), a haze measuring device such as that of Bykgardner can be used. This device consists of a tube located in front of an integrating sphere. Turbidity measurements can be made according to ASTM D1003-7, for example mentioned in EP 1 529 632 A1.

  The temperature and pressure conditions for carrying out the production process according to the invention usually depend on the polymer used and the carrier medium and can therefore vary within a wide range. The polymer melt (a) is usually produced at a temperature of 100 to 300 ° C, preferably 100 to 250 ° C. The preparation (b) is usually performed at a temperature of 0 to 150 ° C, preferably 10 to 120 ° C.

  Mixing of the preparation and polymer melt in step c is usually carried out at a temperature of 100 to 300 ° C, preferably 100 to 250 ° C. This mixing is usually performed in step d at a temperature of 100 to 300 ° C, preferably 100 to 250 ° C. All steps of the process according to the invention can also be carried out at normal pressure (1 atm) and at a maximum of 100 bar or slightly under reduced pressure.

  Of course, one or more polymers can be used, for example in the form of a polymer mixture or blend, to make the polymer melt (a).

  In a preferred embodiment of the method according to the invention, a thermoplastic polymer is selected as the polymer for producing the polymer melt (a).

Contemplated as thermoplastic polymers are oligomers, polymers, ionomers, dendrimers, copolymers such as block copolymers, graft copolymers, star block copolymers, random block copolymers, or mixtures thereof. Generally, a thermoplastic polymer has a mass average molecular weight _Mw of 3,000 to 1,000,000 g / mol. M _w is preferably 10,000 to 100,000 g / mol, very preferably 20,000 to 50,000 g / mol, especially 25,000 to 35,000 g / mol.

  Among the thermoplastic polymers mentioned are first polyolefins, especially polypropylene and polyethylene, polyolefin copolymers, especially ethyl vinyl acetate copolymer, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC). ), Polyvinylidene chloride, polyvinyl alcohol, polyvinyl ester, polyvinyl alkanal, polyvinyl ketal, polyamide, polyimide, polycarbonate, polycarbonate blend, polyester, polyester blend, poly (meth) acrylate, poly (meth) acrylate-styrene copolymer blend, poly (Meth) acrylate-polyvinylidene fluoride blend, polyurea Down, a mixture of polystyrene, styrene copolymers, polyethers, polyether ketones, polysulfones, and their polymers. Preferably, polyethylene, PVC or PVDF is used.

  The polymer melt can be made by any method known to those skilled in the art, for example by melting the polymer. Here, the polymer may be present in the form of powder or pellets before melting. The polymer is preferably present in the form of pellets. Melting is preferably performed in an extruder or calendering machine.

  In order to produce the polymer composition, the process according to the invention comprises in step (b) the preparation of a liquid carrier medium (in which the nanoparticulate IR absorber is dispersed). This means that the carrier medium is liquid at the pressure and temperature conditions used each time in steps (b) and (c). In the context of the present invention, a liquid carrier medium is understood as a carrier medium having rheological properties ranging from a smooth liquid to a paste / cream to a gel. A “flowable compound” usually has a higher viscosity than a liquid, but is not self-supporting, ie it cannot maintain a given shape without a covering that stabilizes the form. In the context of the present invention, the term liquid carrier medium also encompasses a flowable component. The viscosity of such preparations is, for example, in the range of about 1-60,000 mPas.

  The advantage of using a liquid carrier medium in which a nanoparticulate IR absorber is dispersed is usually that no relatively large agglomerates are produced compared to using a solid state (eg as a powder) nanoparticulate IR absorber. A clearly more homogeneous distribution of the nanoparticulate IR absorber in the polymer composition can be achieved. That is, relatively large agglomerates usually lead to undesirably enhanced visible light scattering, and the fine and homogeneous distribution of nanoparticulate IR absorbers leads to improved IR radiation absorption.

  Suitable as the carrier medium are, for example, many organic solvents which are liquid at room temperature and preferably do not react with oxygen. These solvents preferably have a nearly neutral pH value.

Possible carrier media here include, for example, the following:
Esters of alkyl carboxylic acids and aryl carboxylic acids,
Hydrogenated esters of arylcarboxylic acids and alkanols,
Monohydric or polyhydric alcohols,
Ether alcohol,
Polyether polyols,
ether,
Acyclic and cyclic saturated hydrocarbons,
Mineral oil,
Mineral oil derivatives,
Silicone oil,
Aprotic polar solvent,
Or a mixture of these carrier media. The carrier medium is preferably ethylene glycol, glycerin, 1,3-propanediol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, acyclic or cyclic ether, or polyether. Polyols, alcohols with a low boiling point (boiling point below 200 ° C.), in particular 1-butanol, 2-butanol, or hydrocarbons with a boiling point below 200 ° C., or mixtures of the above-mentioned preferred carrier media are used.

  In addition, a possible carrier medium is a wax. Preferably, polyolefin waxes and polyolefin comonomer waxes can be used as carrier media, especially ethylene-homopolymer waxes, montan waxes, oxidized and comminuted PE waxes, metallocene PE waxes, ethylene copolymer waxes such as Luwax®. ) Products, see the product list of BASF SE.

  Carrier media are generally available commercially.

  In a preferred embodiment of the process according to the invention, the carrier medium is liquid in the temperature range from 50 to 120 ° C., preferably from 90 to 110 ° C., at normal pressure. The carrier medium here is in particular PE wax.

  According to the invention, a nanoparticulate IR absorber is dispersed in the preparation from step (b). This means that the nanoparticulate IR absorber is present uniformly and finely distributed in the carrier medium. Such dispersion is obtained by the nanoscale IR absorber forming little aggregates or particles greater than 500 nm. Preferably there are no aggregates or particles greater than 300 nm, very preferably there are no aggregates or particles greater than 200 nm. The particles separated from one another are present, inter alia, at an average distance of at least 200 nm. In one embodiment of the composition from step (b) of the method according to the invention, more than 90% of the particles have an average particle size of less than 200 nm. In a further preferred embodiment, more than 95% of the particles have an average particle size of less than 200 nm. In a further embodiment, greater than 99% of the particles have an average particle size of less than 200 nm. In a further preferred embodiment, less than 10% of the particles, particularly preferably less than 5% of the particles have a minimum distance from the nearest particle of at least 50 nm, preferably at least 100 nm, more preferably at least 250 nm, and especially preferred Is at least 500 nm.

  Here, the particles may have any shape. For example, there can be spherical, rod-like, flake-like particles, or irregularly shaped particles. A nanoscale IR absorber having a bimodal or multimodal particle size distribution can also be used. The particle distribution is examined, for example, with a confocal laser scanning microscope. This technique is described, for example, in “Confocal and Two-Photon Microscopy” edited by Alberto Diaspro; ISBN 0-471-40920-0, Wiley-Liss, a John Wiley & Sons, Inc. Publication, Chapter 2, pages 19-38, and It is described in the literature cited there. The measurement of the particle size (distribution) can also be performed using electron microscopy (TEM).

  Examples of nanoparticulate IR absorbers dispersed in the preparation in step (b) and present in the carrier medium include, for example, carbon black, metal borides, or doped tin oxide in the scope of the method according to the invention. Can do.

IR absorbers are preferably nanoparticulate tin oxide (ATO or ITO) doped with antimony or indium, or nanoparticulate metal borides (MB _x , x = 1-6), especially alkaline earths Metal borides or rare earth metal borides are used. Particularly preferred are nanoparticulate rare earth metal borides. Very particular preference is given to the metal hexaboride of the symbol MB ₆ in particular M being La, Pr, Nd, Ce, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, Ca. belongs to. Likewise preferred metal borides MB ₂ are especially those in which M is Ti, Zr, Hf, V, Ta, Cr, Mo. Further suitable metal borides are Mo ₂ B ₅ , MoB, W ₂ B ₅ . A very excellent IR absorber is nanoparticulate lanthanum hexaboride (LaB ₆ ). Of course, mixtures of the above nanoparticulate materials are also suitable as IR absorbers. Nanoparticulate LaB ₆ is commercially available or can be produced according to the method of WO 2006/134141 or WO2007 / 107407. Nanoparticulate ITO or ATO is commercially available.

  The amount of nanoparticulate IR absorber used can vary over a wide range, for example depending on the ultimate intended use of the polymer composition. Usually, the decisive factor for the effective action of the IR absorber is that when the heat irradiation passes through the polymer composition, the IR absorber absorbs the heat irradiation, so it is sufficiently present at the location where the heat irradiation passes. Is.

  The amount of nanoparticulate IR absorber in the polymer composition is up to 2% by weight with respect to the thermoplastic polymer melt from step a. The amount of IR absorber is preferably from 0.001 to 1% by weight, very preferably from 0.01 to 0.5% by weight and especially from 0.01 to 0.2% by weight.

  The proportion of IR radiation absorbed by the polymer composition will depend on the desired application each time. The polymer composition, for example, absorbs more than 5% of incident IR radiation. Preferably more than 20% of the incident IR radiation is absorbed, very preferably more than 50%.

  In order to produce the preparation in step (b) of the process according to the invention, the liquid carrier material and the nanoparticulate IR absorber are usually mixed with one another. Here, this mixing can basically be carried out by any mixing device known to the person skilled in the art, for example a stirrer, an extruder and a kneader.

  In a preferred embodiment of the method according to the invention for the production of a polymer composition, the preparation of a metal boride-containing composition by in situ plasma synthesis in step (b) is described in unpublished EP 08167612.4. Do as follows. Here a starting material for the metal boride is made, this starting material is subjected to a heat treatment under plasma conditions, the resulting product is quickly cooled and the thus obtained cooled product is put into a liquid (where A suspension is obtained), which can be used directly as a preparation in step (b) of the process according to the invention. Starting materials for metal borides are made, for example, by synthesis from suitable starting materials. The advantage of this approach is that the preparation used is highly pure. Here, for example, grinding body wear which occurs during the grinding process is avoided. This wear can lead to impure preparations by extraneous materials and subsequent turbidity of the polymer composition.

In another embodiment, from step (b) by suitably incorporating at least one metal boride, preferably MB ₆ , especially LaB _6, into the support medium and simultaneously milling, preferably milling. The preparation of This variant can of course use metal borides already present in the form of nanoparticulate particles. The metal boride to be pulverized is preferably used in non-nanoparticulate form. In particular, the metal boride to be pulverized is initially 500 nm to 50 μm, preferably 1 to 20 μm in size.

  Milling is suitable for this purpose, preferably a mill such as a bead mill, a stirred bead mill, a circulation mill (stirring bead mill with a pin mill system), a disk mill, a ring chamber mill, a double cone mill, a three roller device, and Perform in a batch mill (see Arno Kwade, “Grinding and Dispersing with Stirred Media Mills: Research and Application”, Technische Universitaet Braunschweig FB Maschinenbau; Auflage: 1, 2007). If desired, a grinding chamber may be configured with a cooling device for discharging the thermal energy input in the grinding process. Suitable for wet grinding to produce the preparation according to the invention is, for example, a bead mill of Drais Superflow DCP SF 12, a circulating mill system ZETA of Netzsch-Feinmahltechnik GmbH (Selb, Germany) or Netzsch Feinmahltechnik GmbH The company's disc mill.

  For milling, milled bodies made of zircon oxide doped with aluminum oxide, zircon oxide or yttrium are often used. In the scope of the method according to the invention, preferably, when preparing the preparation from step (b), milling of the carrier medium with IR absorber is carried out using a milled body made of aluminum oxide. The advantage of such milling is that the wear that appears in the case of commonly used zircon grinds (this wear usually leads to turbidity of the polymer composition) does not appear.

  Thus, the polymer composition produced by the process according to the invention preferably has a very low content of zircon oxide. Preferably, the polymer composition contains less than 0.2% by weight, particularly preferably less than 0.15% by weight, and zircon oxide.

Thus, in a further preferred embodiment, the polymer composition produced by the process according to the invention comprises nanoparticulate metal borides, preferably MB ₆ , in particular LaB ₆ , 0.001 to 1% by weight, very particularly preferably 0.00. It contains from 01 to 0.8% by weight, and especially from 0.01 to 0.5% by weight, with a very small content of zircon oxide. The zircon oxide is preferably less than 50% by mass, particularly preferably less than 40% by mass, based on the total amount of zircon oxide and nanoparticulate metal boride. Most preferably, the nanoparticulate metal boride has a mass average particle diameter of at most 200 nm, preferably at most 150 nm, in particular from 70 to 130 nm.

  The milling is preferably carried out with the addition of the main amount, in particular at least 80-100% of the carrier medium.

  Depending on the length of time required for pulverization, the desired fineness or particle size of the active substance particles is adjusted by known methods, which can be determined by routine experimentation for those skilled in the art. For example, grinding times in the range of 30 minutes to 72 hours have proven advantageous, but longer durations are also conceivable.

  The pressure and temperature conditions in pulverization are generally not important. Thus, for example, normal pressure has proven to be suitable. For example, a temperature in the range of 10 to 100 ° C. has proven to be suitable, where an increase in temperature usually leads to a reduction in grinding time.

  In order to basically prevent agglomeration and coalescence of the nanoparticulate IR absorber and / or to ensure good dispersibility of the particle phase in the carrier medium, the IR absorber used is surface-modified or surface-coated. be able to. The particles have, for example, a single or multi-layer coating on at least a part of their surface, this layer containing at least one compound having ionogenic, ionic and / or nonionic surfactant groups. . The compound having a surface active group is preferably a salt of a strong inorganic acid such as nitrate and perchlorate, saturated and unsaturated fatty acid such as palmitic acid, margaric acid, stearic acid, isostearic acid, nonadecanoic acid, lignoceric acid, Palmitooleic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid, quaternary ammonium compounds such as tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide, silanes such as alkyltrialkoxysilane, and the like Is selected from a mixture of In a preferred embodiment, the nanoparticulate IR absorber used according to the invention does not contain an interfacial modifier.

  The preparation of the preparation from step (b) is preferably carried out with the liquid carrier medium to be used subsequently by in-situ milling, in particular milling in situ. In particular, the carrier medium is not removed from the preparation after reaching the dispersed state, and the proportion is reduced as much as possible within the range in which the dispersed state is maintained. In some cases, a partial or complete exchange of the carrier medium is carried out by liquid-liquid conversion, while the dispersion is still maintained. The exchange of the carrier medium is preferably no longer carried out after production of the preparation. However, at least one further component compatible with the carrier medium can be added as long as the dispersion is maintained. The addition of one or more additional components can be done before, during or after the preparation of the dispersed preparation. Preferably the preparation obtained by in-situ milling is directly subjected to further processing following its manufacture.

  The solids content of the preparation from step (b) is preferably at least 1% by weight, particularly preferably at least 10% by weight, very particularly preferably based on the total weight of the preparation from step (b) At least 20% by weight, and in particular 20-40% by weight.

  The content of nanoparticulate IR absorber in the preparation from step (b) is preferably at least 1% by weight, particularly preferably at least 10% by weight, based on the total weight of the preparation from step (b). %, Very particularly preferably at least 20% by weight and especially 20 to 40% by weight.

The content of the metal boride, in particular MB ₆ , of the preparation from step (b) is preferably at least 50% by weight, particularly preferably at least 65% by weight, based on the total solid content of the preparation.

  As described above, in step (b), a preparation containing a wax and a nanoparticulate IR absorber dispersed therein can also be used. The mixing of the nanoparticulate IR absorber into the wax is carried out with a mixing device in the usual manner known to those skilled in the art. This mixing can here be carried out using a so-called flash process, for example the method of the unpublished European patent application 08159697.5. Here, the nanoparticulate IR absorber is often present in the form of a dispersion in a polar or aqueous solution. As the mixing device, a batch kneader, a dispersion kneader, or an extruder with a mixing device can be used. Particularly preferably, the nanoparticulate IR absorbent dispersion is mixed in a batch kneader. Here, the temperature of the kneaded material, the amount ratio of the nanoparticulate IR absorber to the wax, the shearing force to be added, and the length of the shearing time are important. When mixing the dispersion of the nanoparticulate IR absorbent into the wax, a temperature program is started, starting at a slightly elevated temperature and continuing to lower the temperature to increase the viscosity of the material. This improves the dispersion result. Preferably, the wax is placed in a kneader to melt and then the nanoparticulate IR absorber dispersion is added in portions or in one portion. The wax can also be charged to the mixing mechanism as a melt. Preferably, a temperature of 50 to 150 ° C is selected. The temperature in the mixing mechanism is particularly preferably 70 to 120 ° C. Whether the nanoparticulate IR absorber has migrated to the non-polar environment of the wax phase is determined by whether the polar or aqueous solvent or water has separated, depending on the temperature, in the form of droplets, or kneaded material Go out as water vapor.

  The phase transition of the nanoparticulate IR absorber from the polar dispersion to the wax results in a composition suitable for step (b) of the process according to the invention. This solvent can be separated from the composition in various ways. The solvent can be drained or evaporated from the mixing mechanism, or the preparation can be removed from the mixing mechanism and optionally optionally ground.

  The preparation is generally pulverized for ease of handling and further processing. Here the preparation can be granulated, pelletized or powdered. For use as a liquid composition in step (b) of the process according to the invention, this composition is of course in the molten state.

  Mixing of the liquid preparation from step (b) and the polymer melt from step (a) is carried out with a mixing device known to those skilled in the art, such as a single screw extruder or co-extruder or a calendering machine. Here, the preparation of the polymer melt in the step (a) can be performed before or simultaneously with the mixing step in the step (c). The polymer melt is preferably made immediately before or during mixing. The production of the liquid composition in the step (b) is usually performed before mixing in the step (c). The prepared liquid composition is preferably added to the polymer melt in one or more steps during mixing in step (c).

  In a preferred embodiment of the method according to the invention, the preparation of the polymer melt (a) and the mixing (c) of the polymer melt with the preparation (b) are carried out by extrusion, injection molding, blow molding, or Perform in the category of the kneading method.

  Preferred in step (c) is the production of the polymer composition by the so-called batch addition method (Masseadditivierungs-verfahren). Specific examples of suitable batch addition methods include extrusion molding, and coextrusion, injection molding, blow molding, or kneading. The liquid composition from step (b) here preferably has a boiling point and / or ignition point above the processing temperature used for the production of the polymer composition. In another preferred embodiment, the liquid composition from step (b) preferably has a boiling point below the processing temperature used to produce the polymer composition and an ignition point above said processing temperature.

  Removal of the carrier medium of the liquid composition from step (b), in particular almost complete removal, is usually not necessary after incorporation into the polymer, which is an advantage of the process according to the invention.

  In the category of the method according to the invention, after mixing in step (c), the polymer composition is processed in step (d). Here, this processing is carried out in accordance with processes known to those skilled in the art, which are customary for plastic processing. The polymer composition can be further processed in step (d) by, inter alia, extrusion, compounding, processing into granules or pellets, extrusion, or processing into a shaped body by coextrusion, injection molding, blow molding or kneading. . The polymer composition is preferably processed into a sheet by extrusion or coextrusion (see Saechtling Kunststoff Taschenbuch, 28. Auflage, Karl Oberbach, 2001).

  A further subject of the present invention is a polymer composition produced by the production method according to the invention described above.

  In a special embodiment, the polymer composition according to the invention or a shaped body produced from said composition comprises or consists of a thermoplastic polymer component. Thermoplastic resins are characterized by their good processability and can be processed into molded parts in the softened state, for example by press molding, extrusion molding, injection molding or other molding methods.

The polymer composition according to the invention can further comprise at least one additive, which is preferably a colorant, an antioxidant, a light stabilizer, a UV absorber, a sterically hindered amine light stabilizer. (HALS), nickel deactivator, metal deactivator, reinforcing material, filler, antifogging agent (antifogging agent), biocide, acid scavenger, antistatic agent, further IR absorption for long wave IR irradiation Agents such as kaolin, anti-agglomeration agents such as SiO ₂ , light scattering agents such as MgO or TiO ₂ , inorganic or organic reflectors (eg aluminum flakes) are selected.

  The total amount of any further additives in the polymer composition is up to 15% by weight with respect to the polymer melt from step (a). The amount of these additives is preferably from 0.5 to 15% by weight, very preferably from 0.5 to 10% by weight, in particular from 0.5 to 7.5% by weight.

  These optional additives can be added in one step of steps (a), (b), (c) and / or (d) during the production of the polymer composition according to the invention, or in any further step of the process. It is added within the range of the following processes. The additive can be added, for example, during the preparation of the polymer melt in step (a), or the polymer used in the polymer melt may already contain the additive. Addition of the additive can also be performed with the preparation of the liquid composition in step (b), in which case the composition already contains the additive. Further additives can also be added to the polymer melt mixture and to the liquid preparation during the mixing in step (c). Additional additives can still be added to the polymer composition during processing (d).

  A molded body can be produced by the polymer composition produced by the method according to the present invention. This molded body can be produced from the polymer composition produced according to the present invention by methods known to those skilled in the art, for example, extrusion molding, coextrusion, injection molding, and blow molding.

  A further subject of the present invention is the use of the polymer composition and the use of the shaped bodies in thermal management. Thermal management includes applications in automobiles, buildings, residences, offices, warehouses, stadiums, airports, or other areas where the heat generated by incident heat radiation is undesirable.

  The polymer composition or shaped body is preferably used in agriculture, especially as a greenhouse sheet. Further preferred applications in agriculture are further agricultural sheets such as silage sheets, roll-up silage sheets, packaging sheets such as stretch and stretch covers, or heavy duty bags.

  A further subject of the present invention is a sheet containing the polymer composition produced according to the present invention, wherein the sheet has 1 to 7 layers, preferably 1 to 4 layers, especially 1 to 3 layers. . The sheet preferably has a thickness of at most 500 μm, preferably 100 to 300 μm, very preferably 150 to 250 μm, in particular 150 to 200 μm. This sheet is typically at least 30 μm thick. This sheet can be produced, for example, by extrusion or coextrusion, for example as described in Saechtling Kunststoff Taschenbuch, 28. Auflage, Karl Oberbach, 2001.

  The shaped bodies according to the invention are preferably used as glazing or roofing materials, agriculture, in particular as greenhouse sheets or as window members.

  Of course, articles, in particular members, having one or more shaped bodies can be produced using the shaped bodies according to the invention. Such members can be used, inter alia, for building thermal management.

  The use of a polymer composition or shaped body according to the invention comprising nanoparticulate IR absorbers enables an effective shielding against heat radiation effects, for example on the surface of buildings, cars or greenhouses. The material enables thermal management of the internal space. In general, the material ensures a high transparency to visible light and at the same time an effective heat radiation interruption, so that the interior space remains bright under sunlight and does not warm as intensely. The increased transparency has a direct positive effect on increasing the yield of plants protected in the greenhouse when using the polymer composition in the greenhouse sheet.

  The present invention will be described in more detail by way of examples, but these examples do not limit the subject of the present invention.

Example:
Example 1:
The description of the production amount of the agricultural sheet having the thermal management function is described in mass% with respect to the total amount of the master batch or sheet.

  Since it is often difficult to add or homogeneously add a small volume of additive to the sheet, the additive is first processed into a masterbatch. This ensures uniform addition of the polymer processed into the sheet over the entire sheet surface and facilitates the process.

The following additives were processed in an extruder into a masterbatch:
Nanoparticulate LaB ₆ , 1.25%, manufactured by in situ plasma synthesis,
Uvinul (registered trademark) 5050H (HALS) 15.0%
Uvinul® 3008 (UV absorber) 7.5%,
Irganox® B 225 (Ciba's Irgafos® 168 and Irganox® 1010 mixture, antioxidant) 2.5%
LDPE (low density polyethylene) 73.75%.

Nanoparticulate LaB ₆ was added to the polymer melt (LDPE) via a liquid feed, and the other components were added as powder or granules.

  8% of the masterbatch, along with 92% of LDPE granules, was placed through a silo into the filling funnel of the extruder, and then these ingredients were processed into a homogeneous plastic composition. The molten polymer was discharged through a nozzle, formed into a sheet blow by an appropriate air flow, cooled and folded into a sheet and wound up.

  These sheets were used in a greenhouse and compared to other greenhouse compartments using standard sheets for temperature evolution.

  When the sheet according to the present invention was used in winter, the maximum temperature during the day could be reduced by an average of 5 ° C. In contrast, at night, temperatures lower by 1-2 ° C. were measured.

  In contrast, during summer daytime, a maximum temperature decrease of 10 ° C. was detected.

  A further sheet having the following composition is produced by the above method.

Example 2:
Sheet composition:
Uvinul (R) 5050H (HALS) 1.0%, Uvinul (R) 3008 (UV absorber) 0.5%, Irganox (R) 1010 0.3%, Irgafos (R) 168 0.2 %, Nanoparticulate LaB ₆ 0.03%, Lupolen® 1840 D (PE) 97.97%.

This sheet reduces IR radiation transmission by up to 50% in the 750-1500 nm wavelength range compared to sheets without nanoparticulate LaB ₆ .

This sheet likewise reduces IR radiation transmission by up to 50% in the wavelength range of 750-1500 nm compared to sheets with agglomerated non-nanoparticulate LaB ₆ particles (particle size eg 1 μm-50 μm). .

  The further sheet compositions of Examples 3-6 also show a decrease in permeability comparable to Example 2.

Example 3:
Sheet composition:
Uvinul (R) 5050H 1.0%, Uvinul (R) 3008 0.5% Irganox (TM) 1010 0.3% Irgafos (R) 168 0.2% nanoparticulate LaB ₆ 0 0.03%, Lupolen® 1840 D 97.97%.

Example 4:
Sheet composition:
Uvinul (R) 5050H 1.0%, Uvinul (R) 3008 0.5% Irganox (TM) 1010 0.3% Irgafos (R) 168 0.2% nanoparticulate LaB ₆ 0 0.0225%, Mark it (R) (antimony compound for laser marking) 0.0075%, Lupolen (R) 1840 D 97.97%.

Example 5
Sheet composition:
Uvinul (R) 5050H 1.0%, Uvinul (R) 3008 0.5% Irganox (TM) 1010 0.3% Irgafos (R) 168 0.2% nanoparticulate LaB ₆ 0 0.03%, magnesium oxide 0.5%, Lupolen® 1840 D 97.47%.

Example 6
Sheet composition:
Uvinul (R) 5050H 1.0%, Uvinul (R) 3008 0.5% Irganox (TM) 1010 0.3% Irgafos (R) 168 0.2% nanoparticulate LaB ₆ 0 0.03%, K1010 (Ni titanate) 0.1%, Lupolen® 1840 D 97.87%.

Claims (27)

The following method steps a. Producing a polymer melt,
b. Producing a preparation comprising a liquid carrier medium and a nanoparticulate IR absorber dispersed therein;
c. Mixing the polymer melt (a) with the preparation (b);
d. Processing the mixture (c);
A method for producing a polymer composition, comprising:   The method of claim 1, wherein the polymer melt contains one or more thermoplastic polymers.   The thermoplastic polymer is polyolefin, polyolefin copolymer, polyvinyl alcohol, polyvinyl ester, polyvinyl alkanal, polyvinyl ketal, polyamide, polyimide, polycarbonate, polycarbonate blend, polyester, polyester blend, poly (meth) acrylate, poly (meth) acrylate- The process according to claim 2, wherein the process is selected from styrene copolymer blends, poly (meth) acrylate-polyvinylidene fluoride blends, polyurethanes, polystyrene, styrene copolymers, polyethers, polyether ketones, polysulfones, polyvinyl chloride.   The method according to any one of claims 1 to 3, wherein the preparation (b) is produced by plasma synthesis of a nanoparticulate IR absorber.   4. The method according to any one of claims 1 to 3, wherein the preparation (b) is made by pulverizing the IR absorber in the carrier medium.   6. The method according to claim 5, wherein the fine pulverization of the IR absorber in the carrier medium is carried out by milling.   7. A process according to claim 5 or 6, wherein the IR absorber is initially used in non-nanoparticulate form for milling.   8. A method according to any one of claims 1 to 7, wherein the nanoparticulate IR absorber has a mass average particle diameter of up to 200 nm.   The process according to any one of claims 1 to 8, wherein the solids content of the preparation (b) is at least 1% by weight, based on the total weight of the preparation (b).   10. The method according to any one of claims 1 to 9, wherein the content of the nanoparticulate IR absorber is at least 1% by weight, based on the total solid content of the preparation (b).   11. The nanoparticulate IR absorber is a metal boride, ATO, ITO, nanoscale carbon black, or a mixture of these substances, according to any one of claims 1 to 10. the method of. The metal boride has the general formula MB ₆
[Wherein M represents a metal component]
The process according to claim 11, characterized in that it is a hexaboride of   The liquid carrier medium is an ester of alkyl carboxylic acid and aryl carboxylic acid, hydrogenated ester of aryl carboxylic acid and alkanol, mono- or polyhydric alcohol, ether alcohol, polyether polyol, ether, acyclic and cyclic 13. Process according to any one of claims 1 to 12, characterized in that it is selected from saturated hydrocarbons, mineral oils, mineral oil derivatives, silicone oils, aprotic polar solvents, or mixtures thereof.   13. A method according to any one of the preceding claims, wherein the liquid carrier medium is selected from polyolefin waxes and polyolefin comonomer waxes.   The carrier medium is ethylene glycol, glycerin, 1,3-propanediol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, acyclic or cyclic ether, polyether polyol, low 14. A process according to claim 13, wherein the process is selected from a boiling alcohol, or a hydrocarbon having a boiling point of less than 200C, or a mixture of the carrier media.   16. Process according to any one of claims 1 to 15, wherein the boiling point and / or ignition point of the preparation (b) is above the processing temperature used for mixing (c).   The process according to any one of claims 1 to 15, wherein the boiling point of the preparation (b) is below the processing temperature used for the mixing (c).   18. Process according to any one of claims 1 to 17, characterized in that the mixing (c) is performed while separating the carrier medium. Additional ingredients in the polymer melt include colorants, antioxidants, light stabilizers, UV absorbers, sterically hindered amine light stabilizers, nickel deactivators, metal deactivators, reinforcements, fillers, antifogging agents. , biocides, acid scavengers, antistatic agents, additional IR absorbers for the long-wave IR radiation, such as kaolin, aggregation inhibitor, such as SiO _2, the light scattering agent, such as MgO or TiO _2, inorganic or organic reflector 19. The method according to any one of claims 1 to 18, wherein an additive selected from is added.   The production of the polymer melt (a) and the mixing (c) of the polymer melt and the preparation (b) are carried out in the category of an extrusion molding method or a kneading method. The method described in 1.   21. A polymer composition produced by the method of any one of claims 1-20.   Use of a polymer composition according to the method of claim 20 in thermal management.   Use of a polymer composition according to the method of claim 20 in agriculture.   Use of a polymer composition according to the method of claim 20 for a greenhouse sheet.   21. Use of the polymer composition according to the method of claim 20 as a silage sheet, a roll-up silage sheet, a packaging sheet, or a heavy duty bag.   21. A sheet containing a polymer composition according to the method of claim 20 having 1 to 7 layers.   27. A sheet containing a polymer composition according to claim 26 or according to the method of claim 20, wherein the thickness is up to 500 [mu] m.